Method of hair conditioning

ABSTRACT

IN WHICH: COSMETIC COMPOSITION COMPRISING, IN A SUITABLE CARRIER, AT LEAST ONE ACTIVE COMPOUND INCLUDING BOTH AT LEAST ONE DISULFIDE FUNCTION AND AT LEAST ONE GROUP RESPONDING TO THE FORMULA:   -N(-R)-CH2-O-R&#39;&#39;   THE NITROGEN ATOM IN SAID GROUP BEING ATTACHED TO A REMAINDER WHICH IS SUFFICIENTLY ELECTROPHILE TO PREVENT THE IMMEDIATE RELEASE OF FORMOL.   R IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, A LOWER ALKYL, A HYDROXY-METHYL OR AN ALKOXY METHYL RADICAL; R&#39;&#39; IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, AND A LOWER ALKYL RADICAL;

United States Patent once 3,694,141 Patented Sept. 26, 1972 3,694,141METHOD OF HAIR CONDITIONING Gregorie Kalopissis, Paris, Jean-LouisAbegg, Le Perreux,

and Guiliana Ghilardi and Henri Philippe de Beaulieu,

Paris, France, assignors to Societe Anonyme dite:

lOreal N Drawing. Filed Aug. 1, 1968, Ser. No. 749,278

Int. Cl. A61k 7/10, 7/06 US. Cl. 8-127.51 3 Claims ABSTRACT OF THEDISCLOSURE Cosmetic composition comprising, in a suitable carrier, atleast one active compound including both at least one disulfide functionand at least one group responding to the formula:

t -N-oHtoR' in which:

R is selected from the group consisting of hydrogen, a lower alkyl, ahydroxy-methyl or an alkoxy methyl radical;

R is selected from the group consisting of hydrogen, and

a lower alkyl radical;

the nitrogen atom in said group being attached to a remainder which issufliciently electrophile to prevent the immediate release of formol.

Keratinic fibers known to consist of chemical substances having a highmolecular weight and having a large number of transverse disulfidebonds. It is considered that these disulfide bonds impart a group ofcharacteristic physiochemical properties to the fibers.

It is also known that the disulfide bonds play an important role in thechemical treatment undergone by hair in order to impart permanentdeformation thereto.

In order to produce such permanent deformation is is necessary to firstopen up the disulfide SS bonds of the keratin, and then, after havingimparted the desired deformation to the hair, to reconstitute the S-Sbonds, usually by means of oxidizing compounds.

On the other hand the chemical processes for imparting a permanentdeformation to the hair, which cause opening of the SS bonds,substantially reduce the percentage of cystine, while other chemicaltreatments such as bleaches or combinations of bleaches and dyes, whichare carried out by using rather strong oxidizing agents, also reduce thenumber of SS bonds in the keratin.

Moreover, atmospheric agents, such as exposure to the sun or sea water,also degrade the hair, to a very substantial extent in some cases.

Such a reduction in the quantity of SS bonds in the hair produces anirreversible alteration in the keratinic structure, which amounts to achange in the strength and cosmetic properties of the hair.

It is for these various reasons that attempts have been made to improveby a cosmetic treatment the quality of hair which has been thusdegraded.

It has already been proposed to strengthen the hair by usingpolysulfhydryl polymers which make it possible to attach polymers ofrelatively high molecular weight to the natural keratinic fibers. Thesepolymers attach themselves solidly to the keratin because they have acertain number of SH groups which can form mixed disulfides withcystein.

It has also been suggested that degraded hair be treated with cosmeticcompositions containing such substances as formaldehyde or othercompounds of this family which attach themselves to the keratin byreticulation, or polycondensation.

The present invention relates to new cosmetic compositions based onactive compounds which increase the percentage of disulfide bonds in thehair.

It is an object of the present invention to provide as a new article ofmanufacture a cosmetic composition characterized by the fact that itcontains at least one compound comprising at least one disulfidefunction and at least one group responding to the formula:

in which:

R represents hydrogen, a lower alkyl radical, a hydroxymethyl radical,or an alkoxy-methyl radical. R represents hydrogen or a lower alkylradical.

The nitrogen atom of said group is attached to a remainder suflicientlyelectrophile to insure the chemical stability of the group, that is tosay, to avoid the immediate release of a formol molecule.

In the present description the term lower alkyl radical is used toidentify alkyl radicals having 4 or less carbon atoms.

In certain particular embodiments, the compositions according to theinvention may contain compounds responding to the general formula:

HOH CQ-(H C) -SS(CH ),,'-Q'--CH OH in which Q and Q, which may beidentical or diiferent, represent nitrogenous groups capable of beingmethylolized, such as ureas, thioureas, amides and carbamates,

n and n, which may be identical or different, each represent a wholenumber less than or equal to 6.

In certain particular embodiments of the invention, the cosmeticcompositions according to the invention may contain at least one of thefollowing compounds:

l;l,N'-dimethylol-dithiodiglycolamide having the for mu a:

N,N' dimethylol-dithiodi(ethylurea) having the formula:

Di(hydroxymethyl acetamido)-dimethyl cystamine am- In this latter methodof producing a self-neutralizing mom'um dichloride having the formula:permanent, or long-lasting set, the compounds according (CHsh (CHMDi(hydroxymethyl-ethylurea)-dimethyl cystamine amto the invention havethe advantage over known commonium dichloride having the formula: poundsof avoiding the formation of mixed disulfides, one

CO (CH3)1 H92 b IH oHloE In a first embodiment of the invention, thecosmetic part of which does not become attached to the keratin.compositions are in'the form of setting lotions which may In effect, byutilizing the disulfides according to the inalso contain an acidcatalyst which facilitates the convention, all the disulfides, that isto say, both the disulfides densation of the methylol groups on thehair. according to the invention, and the mixed disulfides ob- The newcompositions have the advantage of increasing tained from the disulfidesand keratin are bonded to the the number of SS bonds in the keratinicfibers by means keratin at each side of the SS bond through their ofcompounds which penetrate into the keratinic fiber and, methylol groups.because of the methylol groups in the active compounds The cosmeticcompositions according to the invention according to the invention,become chemically attached may take the form of a liquid containing theactive comto the substance of the hair itself. This addition to thepounds in a simple aqueous or hydroalcoholic solution. number of SSbonds permits the formation of mixed These compositions may also takethe form of a cream disulfides between the compounds according to theinor gel with the active compounds dispersed or dissolved vention andcystine, which also strengthens the hair. in one of the phases of thecomposition.

Both the SS bonds added by the compositions ac- The compositionsaccording to the invention may also cording to the invention, and the SSbonds of the contain any other ingredients conventionally used in mixeddisulfides may be used in permanent waving proccosmetology, such asdyes, perfumes, swelling agents, suresses. face-active agents, etc.

Finally, the compositions according to the invention They may also bepackaged as aerosols. have, independently of the additional SS bonds,the ad- The compositions according to the invention contain, vantage ofstrengthening the hair because of the phein general, from 1 to 10% andpreferably 2 to 4% of the nomenon of condensation or reticulation whichis due to active compounds. the presence of the methylol groups. It is afurther object of the invention to provide as In another preferredembodiment of the compositions a new article of manufacture a chemicalcompound which according to the invention, the active compounds areinmay be used in cosmetology characterized by the fact that troducedinto fixing lotions designed to carry out the it corresponds to thefollowing formula:

second step of a permanent Wave. In this case, particular reliance isplaced on the oxidizing properties of the SS functions in the activecompounds according to the invention.

In one particular method of using these compositions, they are employedas fixing lotions when permanently setting the hair, which permits thehair, after having been first reduced, rolled up on setting rollers andthen impregnated with such a lotion to be dried directly.

In this case, the composition according to the invention makes itpossible to not only reconstitute the SS bonds of the keratin, but alsoto strengthen the hair by reticulation or condensation of the methylolfunctions, while Q and Q, which may be identical or different, representeither an aminoalcoylamide remainders which may be quaternized, or aremainders containing urea, thio-urea, or carbamate groups, which mayalso contain an eventually quaternized amine function, the -CH OH groupsbeing attached to the amide nitrogen of these remainders.

n and n, which may be identical or different, each represent a wholenumber less than or equal to 6.

simultaneously increasing the quality of sulfur attached The Pmsfintinvflnfiofl has its Particular i the to the hair. following chemicalcompounds:

In another embodiment, the compositions according to N,N'- im thyloldithi0di(ethylurea) having the the invention are compositions which makeit possible to formula; produce a long-lasting deformation of the hairin a single step, with the reducing and oxidizing phases being carried 0out simultaneously.

It has already been suggested that permanent waves be OHZ-OHPNHCNHCH1OHproduced by using compositions containing a mixture of thiols anddisulfides, in which the molar concentration of the disulfides isgreater than that of the thiols. Di(hydroxymethyl acetamido)-dimethylcrystamine In accordance with the present invention, it is adammoniumdichloride having the formula:

vantageous to use in such compositions the new disulfideDi(hydroxymethyl-ethylurea)-dimethyl cystamine amcompounds hereinbeforedescribed. monium dichloride A further object of the present inventionis to provide several methods of preparing the chemical compounds whichhave just been described.

In accordance with the invention, by starting with a compound alreadyhaving a disulfide bond and at least one amine function, and reactingthis with a cyanate which transforms the amine function into a ureafunction, which is then methylolized with a solution of formaldehyde, achemical compound according to the invention is obtained.

In an alternative method of preparing a compound according to theinvention, the process starts with a halogen derivative having an aminefunction which is transformed into sodium S-amino-alkyl-thiosulfate byreacting it with sodium thiosulfate. This salt may then be hydrolyzed toproduce a disulfide which comprises, like the starting product, at leastone amine function. This amine may be transformed into urea by reactingit with a cyanate, as has just been described, and methylolized by asolution of formaldehyde. The disulfide having a tertiary amine functionmay be quaternized with a compound which is itself methylolized orcapable of becoming so, such as chloracetamide orN-methylol-chloracetamide. In both cases a chemical compound accordingto the invention results.

In order that the invention may be better understood, several examplesof the preparation and use of the active compounds according to theinvention will now be described purely by way of illustration.

EXAMPLE I Preparation of N,N'-dirnethyloldithiodi(ethylurea) An aqueoussolution of cystamine dihydrochloride is reacted with a stoichiometricquantity of potassium cyanate for 2 hours at 80 C.

The reaction yields dithiodi(ethylurea) which is extracted andrecrystallized in absolute ethanol. The melting point of the resultingproduct is between 152 and 153 C. and the yield is 77% A solution isthen prepared which contains one mole of dithiodi(ethylurea) per literof water, to which 187.5 g. of formaldehyde in the form of a 40% aqueoussolution is added. The pH value of the mixture is adjusted to 8 byadding an N/ 10 sodium hydroxide solution and heated while stirring to atemperature of 50 C., while maintaining the pH at a value near 8. Thereactants are completely dissolved at the end of about 30 minutes.

The reaction mixture is then cooled to C. and a white crystallineproduct having a melting point of about 100 C. results.

The yield of the reaction is 70% and the product contains about 20%combined formol.

EXAMPLE II Preparation of di(hydroxymethyl-acetamido), dimethylcystamine ammonium dichloride Beginning with N dimethyl bromoethylaminehydrobromide, sodium S-dimethylaminoethyl thiosulfate is prepared byreaction with sodium thiosulfate, which is then hydrolized to obtain thedisulfide, that is to say, tetramethyl cystamine.

The reaction produces a yield of 50% and a liquid is obtained having aboiling point of 100 C. under a pressure of 1 millimeter, and containing99% of the theoretical quantity of tertiary amines.

The tetramethyl cystamine is then quaternized with a stoichiometricquantity of N methylol chloracetamide.

The reaction is carried out at 100 C. for 30 minutes and a colorlesspaste is obtained which contains no tertiary amines. The yield of thereaction is 100%.

EXAMPLES OF APPLICATIONS Example I A solution having the followingcomposition is applied to hair which has first been washed and dried:

G. Thioglycolic acid 2.5 Di-(hydroxymethyl acetamido) dimethyl cystamineammonium dichloride 7 Monoethanolamine, q.s.p., pH 9.5. Water, q.s.p.,c.

The following composition is applied to hair which has previously beenbleached:

G. N,N'-dimethylol dithiodi(ethylurea) 2 Polyvinylpyrrolidone/vinylacetate copolymer 0.4 Trimethyl cetyl ammonium bromide 0.1

Acetic acid q.s.p., pH 3. Water, q.s.p., 100 cc.

The hair is set in a conventional manner and it is found that the hairis harder and cleaner, and its tips are less dry than when bleached hairis set using a process other than one according to the invention.Moreover, the wave set exhibits excellent resilience.

Example III -A long lasting set is produced in a generally conventionalmanner, using the following composition:

Thioglycerol, 3 g. Ammonia, q.s.p., pH 9.5. Water, q.s.p., 100 cc.

The hair is impregnated with this solution, wound upon setting rollersof the usual diameter, and again saturated with the solution beforebeing left for 15 minutes under a plastic cap at room temperature.

The hair is then rinsed and the following solution is applied:

N,N-dimethylol dithiodiglycolamide, 4 g. Phosphoric acid q.s.p., pH 2.5.Water, q.s.p., 100 cc.

The hair is then placed under a hood and dried in a conventional manner.The resulting wave is of excellent quality and exhibits excellentstability in time.

Example IV The first step of a long lasting set is carried out as inExample II'I after which the following solution is applied to the hair:

N,N'-dimethylol dithio dipropionamide, 4 g. Phosphoric acid q.s.p., pH2.5. Water, q.s.p., 100 cc.

The hair is then placed under a hood and dried in a conventional manner.The resulting wave is of excellent quality and exhibits excellentstability in time.

Example V The following composition is applied to hair which has firstbeen washed and dried:

Thioglycolic acid 2.5 Di(hydroxymethyl ethylurea) dimethyl cystamiueammonium dichloride 7 Monoethanolamine, q.s.p., pH 9.5.

The hair is then wound upon rollers and left under a hood for 15 minutesat a temperature of 35 to 40 C., rinsed with running water, andimpregnated with a solution comprising citric acid to bring its pH to2.5. The waving process is then completed in a conventional manner bydrying it at a temperature of about 45 to 50 C.

The hair exhibits excellent resilience, and the wave is very stable intime.

What is claimed is:

1. A method for strengthening hair comprising applying to said hair inamounts effective to strengthen said hair a composition having a pH of2.5 to 3 and comprising a solution in a solvent selected from the groupconsisting of water and aqueous alcohol solution of an active compoundselected from the group consisting ofN,N'-dimethylol-dithiodiglycolamide,

N,N'-dimethylol-dithiodi (ethylurea) di(hydroxymethylacetamido)-dimethyl cystamine ammonium dichloride,di(hydroxymethyl-ethylurea)-dimethyl cystamine ammonium dichloride, and

N,N-dimethyloldithiodipropionamide, said active compound being presentin amounts ranging from 110% by weight of said composition, and an acidcatalyst selected from the group consisting of acetic acid, phosphoricacid and citric acid, and then drying said hair.

2. A method for permanently setting hair comprising applying to hairpreviously chemically reduced, rinsed and then mechanically shaped, aneffective amount of a composition having a pH of 2.5 to 3, saidcomposition comprising a solution in a solvent selected from the groupconsisting of water and aqueous alcohol solution of an active compoundselected from the group consisting ofN,N'-dimethylol-dithiodiglycolamide,

N,N'-dimethylol-dithiodi(ethylurea) di(hydroxymethyl acetamido)-dimethylcystamine ammonium dichloride, di(hydroxymethyl-ethylurea)-dimethylcystamine ammonium dichloride, and

N,N-dimethylol dithio dipropionamide, said active compound being presentin amounts ranging from 110% by weight of said composition, and an acidcatalyst selected from the group consisting of acetic acid, phosphoricacid and citric acid, and then drying said hair.

3. A method for permanently setting hair comprising applying to hair acomposition having a basic pH and comprising a solution in a solventselected from the group consisting of water and aqueous alcohol solutionof (a) a thiol hair reducing agent in amounts effective to reduce saidhair and (b) an active compound selected from the group consisting ofN,N'-dirnethylol-dithiodiglycolarnide,

N,N'-dimethylol-dithiodi(ethylurea) di(hydroxymethyl acetamido)-dimethylcystamine ammonium dichloride, di(hydroxymethyl-ethylurea)-dimethylcystamine ammonium dichloride, and

N,N'-dimethylol dithio dipropionamide, said active compound beingpresent in amounts ranging from 110% by weight of said composition,heating the air, rinsing the hair with water, impregnating said rinsedhair with a pH 2.5 to 3 solution comprising an acid catalyst selectedfrom the group consisting of acetic acid, phosphoric acid and citricacid and then drying said hair.

References Cited UNITED STATES PATENTS 3,642,429 2/ 1972 Kalopissis etal. 8-127.51 3,485,815 12/1969 Oroslan et al 8-1163 X 2,351,718 6/1944Speakman 8-128 X 2,723,213 11/1955 Powers et al 8-128 X 3,149,042 9/1964 Habicht et al 424- 3,349,000 10/1967 Joos 8127.6 X

GEORGE F. LESMES, Primary Examiner H. WOLMAN, Assistant Examiner U.S.Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,694,141 pated. September 26, 1972 Gregoire Kalopissis; Jean-LouisAbegg; Giuliana Inventor(s) Ghilardi; and Henri Philippe de Beaulieu Itis certified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

In the heading, add

P y, pplication Luxembourg- 5 b 33, .August 2, 196

Signed and sealed this 3rd day of December 1974.

(SEAL) Attest:

McCOY M. GIBSON JR. cw. MARSHALL DANN At-testing Officer Cmmnissioner ofPatents *cmM 5 0-1050 (10-69) uscomm-oc wan-pan

